U.S. patent number 3,841,099 [Application Number 05/407,144] was granted by the patent office on 1974-10-15 for working fluids for external combustion engines.
This patent grant is currently assigned to Union Carbide Corporation. Invention is credited to George S. Somekh.
United States Patent |
3,841,099 |
Somekh |
October 15, 1974 |
WORKING FLUIDS FOR EXTERNAL COMBUSTION ENGINES
Abstract
Water-pyridine mixtures containing about 25 to 90% by weight of
pyridine have been found to be excellent working fluids for
external combustion engines. Methyl substituted pyridines such as
2-methyl pyridine, 4-methyl pyridine, or 2,6-dimethyl pyridine, as
well as 1,2-diazine, 1,3-diazine and 1,4-diazine can be substituted
for pyridine itself.
Inventors: |
Somekh; George S. (New
Rochelle, NY) |
Assignee: |
Union Carbide Corporation (New
York, NY)
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Family
ID: |
26797456 |
Appl.
No.: |
05/407,144 |
Filed: |
October 17, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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100699 |
Dec 22, 1970 |
|
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862526 |
Sep 30, 1969 |
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Current U.S.
Class: |
60/671;
252/67 |
Current CPC
Class: |
F01K
25/10 (20130101); F01K 25/06 (20130101) |
Current International
Class: |
F01K
25/00 (20060101); F01K 25/06 (20060101); F01K
25/10 (20060101); F01k 025/06 () |
Field of
Search: |
;60/36 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Geoghegan; Edgar W.
Assistant Examiner: Ostrager; Allen M.
Attorney, Agent or Firm: Crow; Bernard Francis
Parent Case Text
This is a continuation-in-part of Ser. No. 100,699 filed Dec. 22,
1970 now abandoned which in turn is a continuation-in-part of Ser.
No. 862,526 filed Sept. 30, 1969 now abandoned.
Claims
What is claimed is:
1. Method of converting heat energy to mechanical energy which
comprises heating an aqueous nitrogen-containing hydrocarbon
working fluid, to the vapor state, said working fluid containing
about 25 to 90 percent by weight of a mono-cyclic
nitrogen-containing hydrocarbon selected from the group consisting
of pyridine, 2-methyl pyridine, 3-methyl pyridine, 4-methyl
pyridine, 2,6-dimethyl pyridine, 1,2-diazine, 1,3-diazine and
1,4-diazine, and utilizing the energy of the vaporized working
fluid to perform work.
2. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is pyridine.
3. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 2-methyl pyridine.
4. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 3-methyl pyridine.
5. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 4-methyl pyridine.
6. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 2,6-dimethyl pyridine.
7. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 1,2-diazine.
8. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 1,3-diazine.
9. Method claimed in claim 1 wherein the mono-cyclic nitrogen
containing hydrocarbon is 1,4-diazine.
10. Method claimed in claim 1 wherein the heat energy is converted
to mechanical energy in a Rankine Cycle engine system.
11. Method claimed in claim 10 wherein the working fluid contains
about 50 to 80 per cent by weight of a mono-cyclic
nitrogen-containing compound.
Description
This invention pertains to working fluids for use in externally
heated engine systems and in particular to their use in automotive
Rankine Cycle engine systems.
In another aspect, the invention relates to working fluids in power
systems using all types of engines (such as, for example, turbines
or reciprocating engines) as the prime mover in the power system,
which utilizes a vapor-liquid engine cycle. Rankine Cycle engine
systems and their advantages are described in many textbooks, as
for example, "Engineering Thermodynamics" by J. B. Jones et. al.
pages 598-617, John Wiley & Sons Inc. (1960) which is
incorporated herein by reference.
The following properties are required for a commercially acceptable
working fluid for use in Rankine Cycle engine systems:
1. Low molecular weight
2. Low freezing point
3. High flash point
4. Moderate viscosity
5. Near-vertical saturated vapor line on a temperature-entropy
diagram
6. High thermal decomposition temperature
7. Non-corrosive to Rankine Cycle system hardware.
It has now been found that the criteria delineated above are
satisfied by binary aqueous solutions containing about 25% to about
90% by weight of certain nitrogen-containing normally liquid
hydrocarbons, viz., pyridine, 2-methyl pyridine, 3-methyl pyridine,
4-methyl pyridine, 2,6-dimethyl pyridine, 1,2-diazine, 1,3-diazine
and 1,4-diazine.
Thus the molecular weight of the components of these binary
solutions is no greater than about 100.
The freezing points of these binary solutions lie in the range of
about -65 to about -5.degree.C.
The flash points of these binary solutions lie in the range of
about 35 to about 57.degree.C.
The viscosities of these binary solutions lie in the range of about
0.35 to about 0.55 centipoises at 100.degree.C.
The saturated vapor line of a binary solution containing 74.5 wt. %
of pyridine and 25.5 wt. % of water on the temperature-entropy
diagram of FIG. 1 can be seen to be nearly vertical.
These binary solutions are thermally stable up to temperatures of
about 400.degree.C.
These binary solutions are non-corrosive to steel up to about
400.degree.C.
In contrast neither water alone nor any of the nitrogen-containing
liquid hydrocarbons listed above alone satisfy all of these
criteria which are de rigeur for working fluids in Rankine Cycle
engine systems. Thus for example the freezing point of water
renders it useless for the operation of Rankine Cycle engine
systems in cold weather.
Water is impractical as a working fluid because of its high
freezing point and low vapor pressures near its freezing point.
The corrosive effects of steam on ferrous surfaces at elevated
temperatures have necessitated the use of costly alloys in the
fabrication of the Rankine Cycle system hardware.
The saturated vapor line of steam on a temperature-entropy diagram
deviates considerably from the vertical, as shown in FIG. 5, which
demonstrates cycle inefficiency due to condensation during
expansion.
As shown in FIG. 6, the horizontal slope of the stam saturation
line requires greater relative superheat in steam systems
necessitating operating temperatures of about 800.degree.E. to
1000.degree.F.
The nitrogen-containing liquid hydrocarbons listed above are
unsatisfactory when used alone as working fluids in Rankine Cycle
engine systems because of their low flash points. But even more
important is the undesirable temperature-entropy diagram of these
hydrocarbons as exemplified by pyridine in FIG. 8.
The superiority of the combination of water and these
nitrogen-containing liquid hydrocarbons as working fluids in a
Rankine Cycle system over either component alone is further
demonstrated in FIGS. 7, 9 and 12. It can be seen from these
figures that in respect of the complexity of the equipment
required, aqueous pyridine solutions provide the simplest and most
economical arrangement of mechanical or hardware components. Thus
aqueous pyridine solutions (FIG. 12) require only five mechanical
components, viz., a heat boiler, an engine, a condenser, a hot well
and a pump. Water alone (FIG. 7) however requires seven mechanical
components because of the extra heat boiler and engine. While
pyridine alone (FIG. 9) requires six mechanical components because
of the necessity of using a regenerator.
Although aqueous solutions containing about 25% by weight to about
90% by weight of nitrogen-containing liquid hydrocarbon can be used
in the practice of this invention, it is preferred to use solutions
containing about 40 to about 90 wt. % or even more preferred to use
solutions containing about 50 to about 80% by weight of hydrocarbon
and most preferred to use solutions containing a range of about 55
to about 60% by weight of hydrocarbon.
The compounds which serve as the nitrogen-containing liquid
hydrocarbons in this invention are readily soluble in water, are
chemically unreactive with water, thermally stable up to about
400.degree.C., non-corrosive towards aluminum alloys in particular
and ferrous alloys in general at elevated temperatures, form
aqueous azeotropic solutions whose saturated vapor lines on a
temperature-entropy diagram are nearly vertical, exhibit
satisfactory thermal conductivity and have molecular weights of
less than about 120.
The preferred mono-cyclic nitrogen-containing liquid hydrocarbon
meeting the criteria recited in the preceding paragraph is
pyridine. While pyridine alone has been suggested as a working
fluid for Rankine Cycle engine systems in the prior art, it is
inferior to aqueous pyridine solutions containing about 25 to about
90% by weight of pyridine as will be shown in the discussion which
follows later.
Other mono-cyclic nitrogen-containing liquid hydrocarbon working
fluids which can also be used in the form of aqueous solutions
include 2-methyl pyridine, 3-methyl pyridine, 4-methyl pyridine,
2,6-dimethyl pyridine, 1,2-diazine, 1,3-diazine and 1,4-diazine. It
is to be noted that one cannot arbitrarily follow a homologous
series in choosing satisfactory nitrogen-containing liquid
hydrocarbons for use in the aqueous working fluids of this
invention as evinced by the fact that the following are
unsatisfactory: 2,4-dimethyl pyridine, 2,5-dimethyl pyridine,
3,4-dimethyl pyridine, 3-ethyl pyridine, 4-ethyl pyridine,
4-ethyl-2-picoline, 5-ethyl-2-picoline, and 1,3,5-triazine because
they are either immiscible with water or actually decompose in
water as is the case of 1,3,5-triazine. The prior art also suggests
the use of 1,3,5-triazine alone as a satisfactory motive fluid
which further points up the narrow and unexpected selectivity
required in the choice of mono-cyclic nitrogen-containing liquid
hydrocarbon working fluids which can be used herein.
A particularly important advantage of the working fluids of the
instant invention is that they can be employed in power systems for
self-propelled vehicles and do not give off large amounts of waste
products which would further contaminate the polluted air
surrounding many of our metropolitan areas today. The heating
plants for such systems emit a substantially lower amount of
pollutants to the air than do internal combustion engines. External
combustion engines can employ more air and longer burning times
than the conventional internal combustion engines used today, thus
permitting a much cleaner exhaust.
The basic Rankine Cycle engine system is composed of a boiler to
convert the working fluid from a liquid to vapor and thus impart
working energy, a prime mover to operate from the working energy of
the working fluid, and a condenser to reconvert the spent vapor
back into liquid form. The boiler can be heated in a number of ways
including but not limited to the burning of conventional fuels and
nuclear power. The prime mover can be a turbine engine or a
reciprocating piston engine. In a binary cycle, the condenser can
be a heat exchanger wherein the high temperature fluid is converted
from vapor back to liquid and the low temperature fluid used to
pick up conventional heat energy from this transformation.
Ordinarily, the condenser is water or air cooled.
A high temperature fluid is one which when employed in a binary
cycle possesses a boiling point higher than the other fluid in the
cycle. In like manner, a low temperature fluid of a binary cycle is
one having a lower boiling point than the other fluid of the cycle.
No precise standards can be given for the terms are relative. A
binary cycle can be successfully carried out by using one fluid for
the high temperature end of the cycle and another fluid for the low
temperature end. Thus, a plurality of prime movers, i.e., turbines
or reciprocating engines, can be utilized in the same system. Here,
the high temperature fluid, after passing through a turbine section
in an expanded state, is condensed by counter-current heat exchange
with the companion low temperature fluid. This fluid goes through a
second turbine section, then is condensed with water and pumped
back to the heating unit.
The heating unit in these systems can be a low grade gas combustion
operation such as combustion from natural gas. It can also be a
nuclear heating unit. The function of the heating unit is to
transfer heat to the working fluids to enable them to activate a
prime mover.
Presently, extensive research is being conducted to find
alternatives to the internal combustion engine. Basic Rankine Cycle
systems using turbine expanders and reciprocating engines are being
developed. Steam as the working fluid is being investigated for
feasibility by representatives of the automotive industry. Other
investigators have been studying the use of fluorocarbons as the
working fluid in turbine expanders and reciprocating engines.
Much research is also being conducted today for operational power
systems in space vehicles. Here, the size and weight of the power
system is a primary consideration. The smaller, lighter engine is
permissible when the instant working fluids are utilized to take
advantage of the high efficiencies which they provide.
It is to be emphasized that the invention resides not in any
particular power system or apparatus but rather in a new class of
working fluids which can be employed in a system having an external
combustion engine as its driving force, such as a turbine or
reciprocating engine. The system is enhanced by full utilization of
the properties of the instant working fluids rather than by any
manipulation or readjustment of the equipment used to produce
electrical power.
Temperature-entropy diagrams are used by those skilled in the art
for evaluating working fluid performance in a Rankine Cycle system.
Temperature-entropy diagrams and their significance are discussed
in standard textbooks, such as "Fundamentals of Classical
Thermodynamics" by G. J. Van Wylen and R. E. Sonntag, published by
John Wiley.
The efficiency of the working fluids of this invention is
demonstrated in FIG. 1 which is a temperature-entropy diagram for a
solution of 74.5 wt. % pyridine and 25.5 wt. % of water. This
composition has an average molecular weight of 42.44. The
calculated curve was prepared assuming the properties of the two
components are additive on a molar basis. The experimental curve
was prepared using experimental liquid heat capacities. The
saturated vapor curve is nearly vertical, so that adibatic
expansion of slightly superheated vapors will not produce liquid in
the exhaust of automotive engines operating at steady state.
Compositions of about 75 wt. % pyridine are recommended for use in
environments where ambient operating temperatures can be low, that
is, about -10 to about -40.degree.C.
FIG. 2 is a temperature-entropy diagram for a pyridine water
solution containing 60% by weight of pyridine. Again the saturated
vapor curve is nearly vertical indicating that expansion of
saturated or slightly superheated vapors would result in vapors
that have neither excessive superheat nor excessive condensate. It
is important to note that the pyridine-water composition containing
about 60 wt. % pyridine is about that of the minimum azeotrope.
This azeotropic system is of great practical advantage inasmuch as
it reduces the possibility of pyridine or water becoming separated
and concentrated as such in any part of a Rankine Cycle System. The
other nitrogen-containing liquid hydrocarbon motive fluids of this
invention also enjoy this property of forming azeotropes with
water.
Rankine Cycles are described for water with reference to the
temperature-entropy diagram of FIG. 5.
Point 1 represents the critical temperature. The curve 1-2
represents the saturated liquid. Curve 1-3 represents the saturated
vapor. In the region to the left of curve 1-2, superheated liquid
exists. The region between the two curves contains both saturated
liquid and saturated vapor. The region to the right of curve 1-3
contains only superheated vapor. All of the region above point 1 is
referred to as the supercritical zone. The fluid in this zone is
also superheated. However, supercritical fluid tends to have
properties between liquid and vapor.
FIG. 6 is a temperature-entropy diagram showing Rankine Cycle
operations. Saturated liquid at the condenser temperature and
relatively low pressure is depicted at point A. This liquid is
pumped to the boiler pressure at B by a high-pressure pump. Point B
is slightly above the saturated liquid curve. The pressurized
liquid then passes into the boiler where it is first heated and
then vaporized to point C, where it is all saturated vapor. The
vapor can then be expanded down to the condenser pressure and
temperature at point D by passing through an engine. This engine is
well insulated so that there is little heat loss. The expansion is
then said to be adiabatic and isentropic so that the ideal
expansion is represented by a vertical line on the
temperature-entropy diagram. The vapor present at point D is then
condensed back to point A.
With water, such an expansion is rather impractical and is not done
in real operations. Problems result from the fact that liquid water
is obtained in the expansion of saturated steam. If a turbine
expander is employed, vapor velocities are so high that the water
droplets that are formed actually erode the turbine blades. If a
reciprocating expander is used, the large proportion of water that
is formed tends to remove lubricant from the piston walls. Since
liquid water is a poor lubricant, the reciprocating expander would
wear out quickly.
In an attempt to circumvent these problems the vapor at C can be
moderately superheated to E. However, expansion of E down to F
still results in the same problems, but to lesser degrees. Heating
the vapor from E up to G does not avoid the problems completely.
Furthermore, very high pressures are involved at G, and the boiler
tubing has to be very thick-walled.
In central-station power plants expansion into the liquid-vapor
zone is reasonably well avoided by expanding part-way along EF,
stopping at H and preheating the expanded vapor to I. Expansion of
vapors at I down to J avoids any deleterious proportion of liquid
("moisture") in the exhausted steam. Of course, the essentially
saturated vapor at J is then condensed. The HIJF area is referred
to as a "reheat cycle". It increases the complexity of the power
plant and requires additional investment for boilers and expanders
to get around the problem of liquid in the expander.
It should be noted that expansions down to D, F, H or J are
depicted as ideal expansions in that the expansion lines are
vertical. Real expansions do, however, involve some increase in
entropy. This results from nonidealities in the expander. Thus,
each of the points D, F, H and J would be located to the right of
where they are actually shown in FIG. 6. Nevertheless, points D and
F would still be well in the Liquid-vapor region. Only points H and
J would be safe operating points. A simplified flow diagram of the
system with water as a working fluid is shown in FIG. 7.
FIG. 8 shows the temperature-entropy diagram for a typical organic
compound, pyridine. The envelope leans to the right, and this is
due to the high heat capacity of the liquid. Thus, a considerable
proportion of heat is required to obtain saturated vapor at C'. For
pyridine (as for most organic fluids) the vapor does not have to be
superheated in order to avoid the formation of liquid upon
expansion. In the ideal expansion from C' to D', D' is at the
condenser pressure but slightly higher than the condenser
temperature. If the vapor at D' is sent directly to the condenser,
the small difference in the heat contained in the fluid between
points D' and E' would be lost to the environment.
However, the real expansion from C' actually goes to point F',
which is also at the condenser pressure. Point F' is well out in
the superheat region, and if this fluid is sent directly to the
condenser a considerable amount of heat would be lost to the
environment. Rather than incurring such a loss, it is the usual
practice in such a case to provide an additional heat exchanger
whereby the heat available between F' and D' is recovered by
preheating liquid from B'. This "preheating" step requires an
additional heat exchanger usually referred to as a "regenerator". A
flow diagram depicting such a system is shown in FIG. 9. An
additional disadvantage of pyridine (and almost all other organic
working fluids) is that the number of pounds of working fluid that
must be recirculated is considerably higher than it is for water.
Thus, the pump that pressurizes the fluid from A' to B' requires
considerable power, and this reduces the overall cycle
efficiency.
The temperature-entropy diagram for the preferred working fluid of
the present invention, 40 wt. % water-60 wt. % pyridine, (the
azeotropic composition) is depicted in FIG. 10. It is clear from
the shape of the temperature-entropy curve and the real cycle shown
that this fluid can be used in the basic Rankine Cycle. No
additional regenerator is needed, and no additional reheat cycle is
needed.
FIG. 11 shows a temperature-entropy diagram for a working fluid of
this invention containing 25.5 wt. % water-74.5 wt. % pyridine. The
same basic cycle can be used as that for the azeotrope shown in
FIG. 10. The only difference is that in this case the vapors sent
to the expander need not be superheated to obtain expanded vapors
containing essentially no liquid. The fluids of this invention
shown in FIGS. 10 and 11 can be used in the simple, basic Rankine
Cycle shown in FIG. 12.
With the working fluids of this invention investment requirements
for the Rankine Cycle system tend to be minimized. The simplicity
of the system requires fewer controls and less maintenance. These
factors are major concerns especially for small systems where cost
and simplicity are important.
Water and the mono-cyclic nitrogen-containing hydrocarbons of this
invention form homogeneous, minimum-boiling azeotropes. An
azeotrope is characterized as having the same composition in the
vapor as that in the liquid. This is an unusual property in that in
ideal solutions the lower-boiling component tends to concentrate in
the vapor. By homogeneous it is meant that when the vapor is
condensed, the condensate is a single liquid. The compositions and
boiling points at 1 atmosphere pressure of pyridine and other
nitrogen-containing hydrocarbons of this invention are listed below
in the Table.
TABLE
__________________________________________________________________________
wt. % b.p. of pure compound b.p. of azeotrope nitrogen containing
(.degree.C, atmospheric pressure) (.degree.C, atmospheric pressure)
water hydrocarbon
__________________________________________________________________________
pyridine 115.3 93.0 40.5 59.5 2-methyl pyridine (2-picoline) 129.5
93.5 48.0 52.0 3-Methyl pyridine (3-picoline) 144.1 97.0 60.0 40.0
4-methyl pyridine (4-picoline) 143.3 97.4 63.5 36.5 1,4-diazine
(pyrazine) 115.5 95.5 40.0 60.0
__________________________________________________________________________
The fact that these azeotropes are homogeneous is in contrast with
the vast proponderance of azeotropes which consist of two
immiscible liquids. Another class of azeotropes is homogeneous at
the boiling point, but upon cooling forms two separate liquid
layers. If water is one of the layers and the solubility of the
organic compound in water is low, the water layer will have an
undesirably high freezing point. The azeotropes in the Table above
are homogeneous at the boiling point as well as at lower
temperatures.
FIG. 13 shows the vapor-liquid equilibria in the water-pyridine
system. This is a temperature-composition diagram in which
temperature is plotted as the vertical axis and wt. % pyridine in
water is plotted as the horizontal axis. The lower curve represents
liquid compositions and the upper curve depicts vapor compositions.
The azeotrope is shown at a. In this type of binary fluid the
composition of the vapor in equilibrium with any liquid tends to
approach that of the azeotrope. For example, composition b which is
high in pyridine is in equilibrium with vapor having composition
b', which has more water than b and is closer to that of the
azeotrope than is b.
In a similar manner, composition c, which has less pyridine than
the azeotrope, is in equilibrium with vapor having composition c'.
The vapor has more pyridine than c. This relationship is important
and is to be contrasted with the situation in an ideal system
illustrated in FIG. 14. In this case the analogous composition at e
is in equilibrium with e'. The vapor e' contains less of the
high-boiling component than e. As a matter of fact e' contains
hardly any of the high-boiling component. If the low-boiling
component has a high freezing point, condensing and then cooling
composition e' could lead to a serious freeze-up problems. This is
to be compared to effect in FIG. 13 where, as a result of the
formation of an azeotrope the vapor c' actually contains an
increased pyridine concentration.
The increased pyridine concentration reduces the freezing point of
condensed water vapor. This is an important discovery since in
air-cooled Rankine Cycle systems, such as automobiles, vapors of
the working fluid are present in the hot well, vapor generator,
expander, piping, and condenser. The vapors throughout the system
condense after a shut down, as the system cools. If water is the
working fluid, its condensate can freeze and can cause serious
blockages that would prevent the system from functioning after
attempts are made to restart the system. However, with
water-pyridine compositions on either side of the azeotrope, this
possible freezing problem does not exist.
A second point to note is that a problem well-known in central
station steam power plants is vapor-phase corrosion. Low-boiling
acidic compounds that can build up in the recirculating working
fluid leads to this vapor phase corrosion. The discovery that
pyridine is an excellent corrosion inhibitor for water is useful in
the vapor state, since the pyridine content of the vapor will
always be high in the vapor. Thus pyridine in the vapor will
neutralize the corrosivity of the acids in the vapor, and this is
an important advantage resulting from the azeotropy.
A third point of considerable importance resulting from the
azeotropy is that the composition of the working fluid will not
change very much, if a vapor leak develops in water-aromatic
nitrogen-containing hydrocarbon fluids. For example, the vapor in
equilibrium with 30 wt. %- 70 wt % pyridine (point d on FIG. 13)
has about 39 wt % water-61 wt. % pyridine (point d'). In FIG. 14 it
can be seen that in an ideal system, point f' has a drastically
different composition than point f at a 70 wt. % high-boiler
content.
Leakage can be a very serious problem, since it is almost
impossible to completely prevent leaks in Rankine Cycle systems.
Leakage of vapor at composition f' would very quickly deplete the
main working fluid of its low-boiler content. The fluids of the
present invention do not have this deficiency. As a matter of fact,
at the azeotropic composition (point A, FIG. 5) there is no problem
at all.
FIG. 3 depicts a comparison between the vapor pressure curves of a
pyridine-water solution containing 60% by weight of pyridine, water
alone and pyridine alone. The fact that the curve for the
pyridine-water solution remains higher than that of water alone or
pyridine alone is important because it is highly desirable to
maintain high pressures at low temperatures to minimize the vacuum
in the Rankine Cycle System when it is cooled thus preventing air
leakage into the condenser of the engine upon cooling. It was also
observed that the vapor pressure curve for this solution is nearly
the same as that for a pyridine-water solution containing 74.5 wt.
% pyridine. This fact is useful in that the Rankine Cycle System
need not be changed if a user decides to change fluid compositions
in order to obtain a lower freezing point fluid. This constancy of
vapor pressure holds true over a wide compositional range namely
from about 25 wt. % to about 90 wt. % of pyridine in
various-pyridine-water solutions. This phenomenon is surprising
because it would be unexpected from a general application of
Raoult's Law.
FIG. 15 demonstrates that 25 wt. % water-75 wt. % pyridine (a
composition close to that of the azeotrope) and 40 wt. % water-60
wt. % pyridine (the azeotrope) have essentially the same vapor
pressure curve. Referring back to FIG. 13, it is apparent that at 1
atmosphere pressure the boiling point is about the same over the
very broad range of from about 20 weight pyridine to about 90
weight pyridine. The data of FIG. 15 lead to the conclusion that in
the same broad composition range the vapor pressure as a function
of temperature is not appreciably different.
This phenomenon is most unusual in that in an ideal solution at a
set temperature the vapor pressure increases as the concentration
of low-boiling component increases. Binary systems having constant
vapor pressure result when the two components are partially soluble
in each other. Thus, the phenomenon of constant vapor pressure
versus composition for the fluids of the present invention are
unexpected, because pyridine, for example, and water are completely
soluble in each other at all temperatures.
This is an important discovery for a Rankine Cycle working fluid.
In moderate climates it is preferred to employ the azeotrope; i.e.,
40 wt. % water 60 wt. % pyridine which has a pour point of about
0.degree.F. However, for extremely cold climates, it is desirable
to increase the pyridine content so as to obtain a lower freezing
point. For example, 25.5 wt. % water-74.5 wt. % pyridine has a pour
point of about -40.degree.F. Employing the working fluids of the
present invention, the Rankine Cycle system need not be redesigned
when the fluid composition is changed, since the vapor pressure in
the boiler does not change, and the vapor pressure in the condenser
does not change.
The vapor pressure of water and a mono-cyclic nitrogen-containing
hydrocarbon of this invention is higher than either component by
itself. FIG. 15 shows that the curve for water-pyridine tends to be
above those of both water and pyridine. This is unexpected, since
in ideal solutions the vapor pressure would lie somewhere between
the vapor pressures of the two components. The synergism of
increased vapor pressure is not much higher at high temperatures,
but is of great advantage at low temperatures.
FIG. 15 shows that even though the vapor pressure of water-pyridine
is considerable higher than that of water at low temperatures, the
pressures at the high temperatures on the boiler, i.e.,
300.degree.C. and higher become almost equal. Thus excessive system
pressures are not obtained with the working fluids of this
invention compared to water, and this is unexpected considering the
relatively higher pressures at low temperatures.
One of the problems with Rankine Cycle systems using steam-water is
that when the system is shut down and the liquid water cools down
near its freezing point, the pressure in the system becomes very
low and this increases the chances of air leaking into the system.
The presence of air in the system is undesirable because it impedes
the proper operation of the condenser. The oxygen in the air can
also lead to serious decomposition of working fluid and lubricant.
The oxygen can also lead to serious corrosion problems.
Referring to FIG. 15 it can be seen that at low temperatures the
pressure in the system with the working fluids of this invention
would be considerably higher than it would be with water. Thus, at
40.degree.C. water has a vapor pressure of 1.07 psia. However,
water-pyridine has a vapor pressure of 1.50 psia, and this is 40%
higher than that of water. This difference becomes even more
remarkable as the freezing point of water is approached. This,
then, is another important synergistic effect of the working fluids
of this invention.
FIG. 4 demonstrates that although the thermal conductivity of water
is higher the thermal conductivity of aqueous pyridine is superior
to pyridine alone.
The thermal stability of a pyridine-water azeotrope containing 57
wt. % of pyridine was demonstrated by heating such a solution in a
stainless steel, high-pressure, rocker bomb under nitrogen for 24
hours at 300.degree.C. and 400.degree.C. respectively. In both
experiments it was found that pyridine decomposition was
negligible.
Using the same rocker bomb, the excellent corrosion properties of
the same pyridine-water azeotrope was demonstrated by charging
coupons of rust free 1010 carbon steel and oxide free 6061 aluminum
together with the azeotrope. A temperature of 400.degree.C. was
maintained for 168 hours. The steel was found to blacken and its
corrosion was measured as being about 1.65 mils per year. The
aluminum formed a very stong protective film that could not be
removed even by scrubbing with 5% aqueous phosphoric acid. The
pyridine degraded to the extent of only about 1.7% of that
originally present. When the same experiment was repeated with the
exception that aluminum was omitted from the rocker bomb, the
corrosion rate of the steel coupon was found to be 1.6 mils per
year and only 0.5 % of the pyridine originally present
decomposed.
In order to simulate condenser corrosion, coupons of 1010 carbon
steel were placed in round bottom flask covered with pyridine-water
azeotrope containing 57 wt. % pyridine and the system boiled at
atmospheric pressure under total reflux for 72 hours. It was found
that the corrosion rate for the carbon steel was 1.4 mils per year.
The pyridine solution was observed to be clear and colorless. As a
Control 1010 carbon steel coupons were exposed to boiling water for
72 hours and it was found that the corrosion rate of the steel was
3.0 mils per year.
For most solutions of liquid organic chemicals in water, the flash
point of the liquid does not increase very much with the addition
of water. It is only after large proportions of water are added
that the flash point increases to a high level. Thus, adding 10, 20
or even 30 wt. % water to methyl alcohol does not raise the flash
points very much, and the flammability of the methyl alcohol is not
reduced significantly.
On the other hand, addition of about 30 wt. % water to pyridine
raises the flash point by 35.degree.F. The very high increase in
the flash point with relatively small additions of water is
unexpected, and is an advantage of this working fluid.
It is thus readily apparent that the aqueous mono-cyclic
nitrogen-containing hydrocarbon working fluids of this invention
are superior to prior art compositions in that they exhibit
excellent temperature-entropy curves and a single vapor pressure
curve, possess lower freezing points than water alone, form
azeotropes which afford the same composition in either the liquid
or the vapor state and inhibit the corrosive properties of water on
steel.
Although the invention has been described in its preferred forms
with a certain degree of particularity, it is understood that the
present disclosure of the preferred form has been made only by way
of example, and that numerous changes and details may be resorted
to without departing from the spirit and scope of the
invention.
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